Preparation of benzanthronyl selenoethers



Q Patented Apr. 30, 1935 I I r V i I 1,999,996 PREPARATION OF BENZANTHRONYL 'SELENOETHERS 7 Melvin A. Perkins, Milwaukee, Wis.,- assignor to E. I. du Pont de Nemours &Company, .Wilmington', Del., a corporation of Delaware UNITED STATES PATENT ori ce-f No Drawing. Application December-20,1933; 7 r. Serial No. 703,251

solai'ms. (omen-s1) This invention relates to a new and improved 'Upon cooling and filtration, a nearly quantitaprocess for preparing selenoethers of-the benzantive yield of 132.1, Bzl ben'zanthronyl selenidefis throne series. 1 obtained. (Recryst. fromj nitrobenaene-M. P.'

In U. S. Patent 1,924,456, a method for pre- 386-? C.) 5 paring benzanthronyl selenoethers is described, in

which selenium and aBzl-halogen-benzanthrone r V p 1 are heated together in a suitable solvent such as 1 part of Bzl-benzanthrone-sodium 'selenolate kerosene or tetrahydronaphthalene. 'is boiledin 6 partsof nitrobenzene'for about 8 7 In my copending application Ser. No. 661,583, I to 10 hours, Upon cooling, filtration and wash- 10' have described a process for preparing symmetriing with alcohol and water, a yellow-brown solid 10 cal selenoethers which comprises reacting a Bzl-- is obtained. It gives an intense green-blue halogen-benzanthrone with alkali-metal selel f l i Sulphuric id a d S- d nt ca t nides or alkali-metal p olyselenides in alcoholic or the product 'of Example 1. 3 aqueous alcoholic solution or suspension; while, x m I m in my copending application Ser. No. 703,248, an j, j I f improvedprocess for the preparation of symmet- 10 parts of'Bz1',BZ1'b y1 se d rical or unsymmetrical benzanthronyl selenoare introduced t 190 Parts Of high b0i1ing keroothers is described, which comprises condensinga Selle po t Of initial reflux about 190 C.) and halogen-benzanthrone with a benzanthronyl the mixture heated to 185-190" C. for several selenide, selenol or diselenide. V hours. At first the mass thickens rapidly, with 20 I have now discovered that symmetrical benthe pp a e of an Orange Solid, little Change zanthronyl-selenoethers may be produced by the being noticeable thereafter. The initial solid deselenation of substituted or unsubstituted'benwhich gives a dull, dark blue coloration'in sulzanthronylselenols, selenoilates or diselenides by phuric acid is gradually displaced by a solid v I was; 2 4

heating them in a suitablesolvent with or without which gives intense bluish-green or greenish-blue 25 the addition of an acid binding agentor a sele- CO OIat S i Sulphuric and the 8nd the m removing m t l, such as copper. During this reaction may be estimated by this color test, heat-. reaction, one atom of selenium is removed from ing being" continued until no further change the diselenides; alkali-metal selenide is removed occurs; The Bzl,Bzl'-benzanthronyl selenoether in the case of the selenolates, and hydrogen produced may be isolated for example by filtering selenide is removed when the selenols are used. from the kerosene, stean'iing the cake and boiling Any suitable solvent may be substituted for with dilute sodium sulphide solution to remove those hereinafter mentioned, so long asthe reacfree selenium and any unchanged diselenide, both tion temperatures, in the neighborhood of 170 or of which dissolve in the sulphide solution and are 5 above, may be attained. filtered from the residual selenoethe'r;

While it is desirable to use acid binding agents such as sodium acetate, calcium hydroxide, so- Example 4 a dium bisulfite, sodium carbonate, etc. when work- 0 Parts Of 2-dich1or0-Bz1,Bz1bening with the selenols, they may be omitted in the zanth l di nid p pa d o xa pl by 40 deselenation of the diselenides or alkali-metal air oxidation of an aqueous solution of the soluble 40 v selenolates'. a reaction product of an alkali selenide and 321,- Without any intention of being limited thereby, BZ2-di0hl01'0-benzanthr0ne 5 Cl) the following specific examples are given to more are heated to 190200 C. in 100 parts of hi fully illustrate the principles of this invention. b iling kerosene until. no u th r cha takes The parts sed are by weight, place. The coloration of the original solid, when 45 Example 1 I j dissolved in sulphuric acid, is violet-brown, while that of the reaction product is blue.v The product 12 parts of Bz1,Bz1'-benzanthronyl diselenide may be'isolated as in Example 3. It is further (M. P. about. 240 C.) and 2 parts of anhydrous differentiated from the starting material in that sodium acetate are slurried in 120 parts of o-di it is not dissolved by sodium sulphide solutions, in chlorobenzene and the mixture heated to reflux that it contains but one atomic proportion of for about 9 hours. At the end of this time, a test selenium and in that alcoholic potassium hyportion shows a bright, strong, green-blue coloradroxide fusion gives an intense blue melt of a dyetion when dissolved in concentrated sulphuric stuff giving strong violetdyeings, apparently a "acid. r I chlorine-containing isoviolanthrone. 5

, Example 5 If 6,6-dibromo-Bz1,Bz1-benzanthronyl-diselenide, prepared iorexample by aeration of the alkali-soluble reaction product of potassiumselenide and 6,Bzl dibromo-benzanthrone (M. P.

257 C.) is. substituted for the startingmaterial in Example 4, similar deselenation takes place.

Since the sulphuric acid solutions of diselenide and selenoether are very similar (greenish-blue and bluish-green respectively) this cannot be used to test the endof thereaction, but instead,

the boiling is continued until a sample of the solid is all, or nearly all, undissolved by warm sodium sulphide solution. The final product is apparently. 6,6'-dibromo-Bz1,Bz1-benzanthronyl selenide and gives, upon alcoholic caustic potash fusion, a blue melt of a dyestufi which dyes cotton very bluish-violet shades from ablue-violet vat.

1 i Example 6" a If 'Bz2,Bz2T-di(acetylamino)-Bzl,Bz1%benzanthronyl diselenide, prepared byfaeration of an aqueousf solution of the'soluble reaction product.

of potassium selenide and Bzl-chloro-BzZ-acetylamino-benzanthrone '(M. P. 272-274 '6.) is substituted for the starting materialin Example 4 and the mixture fboil ed11.85 190 C.) for ten hours, a brownish-yellow solid is obtained. It gives a brownish-red coloration in sulphuric acid (yellowish or greenish fluorescence), is insoluble in hot sodium sulphide solutions, and when fused in' alcoholic-caustic potash yields a bluish-green melt of a dyestufi which yields water-fast greenish-blue dyeings from a bright blue vat, and

which is probably diamLno-isoviolanthrone..

Example 7 10 parts of the diselenide, obtained by aeration of the soluble reactionproduct of potassiumselenide and beta,Bzl-dichlorm-benzanthrone (prepared by chlorination of the more soluble fracthe mixture boiled for some time,',filtered, and the solid washed and 1 dried. The diselenide used as starting material gives a dark brownishviolet solution in sulphuric acid'fan intense redviolet solution in sodium sulphide solution and 9 an olive melt in alcoholic caustic potash, no real dye being formed. In contrast, the reaction product gives an intense dark blue solution in sulphuric acid, is not soluble in sodium sulphide solutions and gives in alcoholic caustic potash, a violet-blue melt of a dye-stuff which gives strong bluish-violetvdyeings from a dark violet vat.

While in the specific examplesabove given only the use of the diselenides'and alkali-metal selenolates has been disclosed, Bzl-benzanthronyl-selenol may also be used in place of the diselenides or selenolates. It is of course understood that either sodium or potassium selenolates maybe converted to the selencethers by this process.

By this process, substitutedBzl,Bzl-benzanthronyl diselenides, Bzl-benzanthronyl selenols or selenolates may belconverted to the selenoethers in the same manner as the unsubstituted compounds, for the use of reagents which might tendto split oil? the substituents are not necessary in this reaction.

In the following claims the terms a Bzl,Bz1'- benzanthronyl diselenide, a Bzl-benzanthronyl alkali-metal selenolate or a Bzl-benzanthronyl-selenol are used to indicate these compounds as such or when they contain other monovalent substituents.

I claim: p

1. In the preparation of Bz1,Bz1'-benzanthronyl-selenoethers the step which comprises heating to reaction temperatures a compound of the group consisting of a Bz1,Bz1'-benzanthronyl diselenide, a Bz1-benzanthronyl-alkali-metal selenolate and a Bzl-benzanthronyl selenol in a solvent. Y

2 In the preparation of Bz1,Bz1-benzanthronyl-selenoethers the step which comprises heating a compound of the group consisting of a Bz1,Bzl-benzanthronyl diselenide, a Bzl-benzanthronyl-alkali-metal selenolate and a Bzlbenzanthronyl selenol in a solvent at temperatures above1'70 C.

3. In the preparation of Bzl,Bz'l'-benzanthronyl-selenoethers the step which comprises heating a Bz1,Bzl'-benzanthronyl diselenide in a solventat temperatures above 170 C.

4. In the preparation of Bzl,Bzl-benzanthronyl-selenoethers the step which comprises heating a B'zl-benzanthronyl-alkali-metal selenolate in a solvent at temperatures above 170 C. I

5. In the preparation of Bz1,Bz1-benzanthronyl-selenoethers the step which comprises heating a Bzl-benzanthrone selenol in a solvent and in the presence of an acid binding agent at temperatures above 170 C.

MELVIN A. PERKINS. 

